Assistants for the textile and related industries



Patented Aug. 21, lose I 1,970,578

UNITED STATES PATENT OFFICE ASSISTANTS FOR THE TEXTILE AND RELATEDINDUSTRIES Conrad Schoeller and Max Wittwer, Ludwigshafen-on-the-Rhine,Germany, assignors to I. G. Farbenindustrie Aktiengesellschaft,Frankiort-on-the-Main, Germany No Drawing. Application November 24,1931, Serial No. 577,148. In Germany November 29, 1930 15 Claims. (Cl.260-98) The present invention relates to assistants for icles into thecarboxylic acids correspond to the the textile and related industries.eneral formula We have found that valuable products are obtained byintroducing into any water-insoluble R'CO OC2H4*) OCH2CH2 OH Organic mpnd c nt n at least one rcin which RC0 is the acid radicle of thecarboxylic 55 active hydrogen atom, i. e. at least one hydroxyl, acidand is 3 or any integral number greater carboxyl amino group, polyglycolTadiclesi than 3. Instead of the acids their esters with having at a tur I XY polyhydric alcohols may be employed in which O p a f0 e a p ethe t tra-ethylene glyc case a reesterification occurs, or the estersmay radiclei be employed which still contain free hydroxyl 60 groups ina polyhydric alcohol radicle of such -e r 2- zz z ester, as for examplemonoor di-glycerides. In-

stead of the said acids or esters the carboxylic any free hydroxylgroups still present being neuhalides of the aforesaid acids may beemployed if tralized with reactive compounds, if desired, as an alkalinecondensing agent be used, or an al- 5 for example with carboxylic acids,polybasic minkaline condensing agent capable of assisting the oral acidssuch as sulphuric acid or phosphoric splitting ofi of halogen in theform of halogen acid, acid halides, alkyl or aryl halogen hydracidhydracids may be employed in the case of emor sulphuric acid esters oraldehydes. As initial ploying ethylene halogenhydrins instead ofmaterials may be mentioned all water-insoluble ethylene oxide. Alcoholscoming into considera- 7 organic compounds which contain one'or moretion are those containing at least 6 carbon atoms equal or difierentgroups of the said kind. For and especially those corresponding to, orpreexample water-insoluble carboxylic acids, alcopared by reduction.from, the aforesaid vegetal hols, phenols, hydroxy carboxylic acids,carboxcarboxylic acids or their glycerol esters, as for ylic acidamides, amines containing at least one example hexyl, octyl, decyl,undecyl, dodecyl, reactive hydrogen atom and any water-insolubletetradecyl or octodecyl, cetyl or oleyl alcohols, hydroxy-alkyl aminesand their water-insoluble cholesterol, and glycols of high molecularweight derivatives are suitable. of the type of octodecandiol, such asoctomethyl Specific examples of the said compounds conglycol ordecamethyl glycol, as well as water-intaining a reactive hydrogen atomare aliphatic soluble alkyl, or also cycloalkyl, aralkyl or aryl, ucarboxylic acids insoluble in water such as those others of thediiferent polyhydric alcohols as for containing at least 6 carbon atomsand especially example the cresylic, phenylic, benzylic, cyclothesaturated, unsaturated and/ or hydroxylated hexylic or naphthylic ethersof glycol or of glycerrboxylic a ids of veg al, i. e. animal and v 01.The products obtainable by introducing the l in. and oth r m n o ply-carboxylic said polyglycol radicles into the said alcohols acidscontaining from 6 to say 30 carbon atoms as correspond to the generalformula for example caproic acid, lauric acid, oleic acid, ricinoleicacid, linoleic acid, palmitic acid, stearic C"H2+1 O C2H4) O Gib-CH2acid, hydroxy stearic acid, montanic acid and in which n is 6 or anyintegral number greater 40 naphthenic acids, as well as analogoussynthetic than 6 and :c is 3 or any integral number greater mixtures,obtainable by the destructive oxidation than 3. Water-insoluble phenolsmay also be of D fi WaX 0 parafiin oil or like non-aroemployed as forexample the isomeric xylenols matic high molecular hydrocarbons andfractions and xylorcins (dimethyl dihydroxy benzene). of such oxidationproducts, as for example the Amines may be chosen from anywater-insoluble 45 hydrozwcarboxylic acid fraction, insoluble inpeamines provided theycontain at least one reactive troleum ether, andthe acids of waxes of vegetal hydrogen atom connected to a nitrogen oroxygen and mineral origin such as of beeswax or Montan atom, as forexample decylamine, undecylamine, wax which contain esters of carboxylicacids with dodecylamine, tetradecylamine, cetylamine, 0cmup to about 30carbon atoms. The products obdecylamine, pentadecylamine,di-heptylamine, di- 50 tainable by introducing the said polyglycolradbutyl amine and diphenylamine. The products obtainable by introducingthe said polyglycol raderalformula' I I I R.NH- (-O.C2H4-.):-OCH2-CH2+-OH in whichRNHis theradicle of the amine and a:

icles' into the said amines correspond to. the genis B'orany integralnumber greater than 3. 'The amines containing a reactive hydrogen atommay contain the latter connected to oxygen as is the case with thealkylol amines which therefore need not contain a hydrogen atomconnected to nitrogen. Suitable amines of this class are for exampleN-cyclohexyl-N-monoor di-alklyol amines such as N-cyclohexyl-N-monoor(ii-ethanol or propanol amines or the corresponding monoorwater-insoluble amides may be chosen from those prepared from ammonia orwater-soluble primary amines and from alkylol amines, asior'example.from those of mono-, dior tri-ethanol or -pro-.

panol amines or of 'mixtures thereof. Waterinsoluble esters of thesealkylol amines with the aforesaid high molecular acids may be employedprovided they still'contain a reactive hydrogen 7 atom as is the casefor example with esters of the type of tri-ethanol amine or (ii-ethanolamine.

di-stearic or -pa1mitic-'esters, the former of which ed to the nitrogenatom.

' I The long chain polyglycol radicles may beadded on to the saidinitial materials by treatment with corresponding quantities of ethyleneoxide or substances forming the same, such as alkylene halogenhydrins,if desired with the employment of condensation catalysts such as surfaceac tive substances as for example bleaching earths or active charcoal,strongly acid substances as for example sulphuric or phosphoric acids orsodium or potassium bisulphates, or also strongly alkaline agents suchascaustic soda or alkali metal alcoholates and/ or with the employment ofincreased pressure, if desired at elevated temperatures such as fromabout to 200 0., preferably between and 150 C. whereby the ethyleneoxide molecules arrange themselves with the formation of long chainpolygylcols. Depending on the amount of ethylene oxide employed it ispossible to add on four or more -C2H4-- groups to each other by means ofether linkages. On the other hand the quadruple polyglycol ethers or theethers containing more than 4 polyglycol radicles may be first formed inknown manner and then condensed in known manner with the compoundscontaining reactive hydrogen atoms to form therewith esters, ethers andso on. If desired mono-alkyl or -aryl ethers or esters of the at leastquadruple polyglycol ethers may be employed for this step so that afurther conversion of the products with acids, acid halides, alkyl oraryl halides or polybasic mineral acids described above may be dispensedwith. .The quantities of the polyglycol forming agents e. g. of ethyleneoxide, or of an equivalent compound such as the glycol chlorhydrins,generally correspond to from one half molecular proportion of polyglycolforming agent per carbon atom of the water-insoluble comcompounds.

pound,the quantity of polyglycol forming agent being,however, at least 4molecular proportions of the water-insoluble initial material even itthe latter should contain less than 8 carbon atoms so that products withat least quadruple polyglycol radicles are formed. In most cases,however, from 6 to 20 and up to 50 molecular proportions or'thepolyglycol forming agent are employed per molecularproportion of thewater insoluble initial material, or the corresponding polyglycolsthemselves.

By employing initial materials containl ing several reactivehydrogenatoms such as glyools, for example octodecandiol,octomethyl glyI I col, decamethyl glycol, or hydroxy carboxylic acids, for examplehydroxy stearic acid and mono-,

glycerol esters thereof, dicarboxylic acids such as I p I sebacid orpimelic acids, or primaryaminesprodc ucts may be obtained containing notonly one but several, at least quadrauple, polyglycol radicles 5 in themolecule. I

' The products obtainable by adding the polygly col radicles on towater-insoluble organic compounds containing at least two of the saidreac- I tive groups usually contain one or two free hydroxyl groups atthe end of the chains and-these may be converted as mentioned with.reactive I As such reactive compounds may be mentioned in particularacids which reactto form esters, as for example sulphuric,chlorsulphonic, phosphoric, phthalic or fatty acids for example withfrom 8 to 1'8 carbon atoms and their derivatives, such as chlorides, orhalogenatedparaffin wax.- Such products as contain a halogen at the endof the polyglycol etherchain 10 as for example those prepared withethylene ox- ,ide andhalogen 'hydrins, or those prepared by substitutingthe hydroxyl group at the end of the chain'by iodineor bromine accordingto the persing in water and have in many cases excellent wetting,foaming and cleansing power so that they may find a wide field ofemployment for example in the textile, leather, paper, wax and polishindustries, as for example in carbonizing, mercerizing, dressing,bucking, washing, finishing, dyeing, printing or polishing. In dyeingand printing they exert an excellent levelling action. For example indyeing with vat dyestuifs, or with azo dyestuffs from fi-naphthoic acidarylides on the fibre, the dyeings are rendered uniform or,respectively, fast to rubbing. A special advantage of the said productsconsists in the fact that they are generally speaking practicallyneutral so that the fibres are in no way attacked. Moreover, theformation of insoluble calcium or magnesium compounds such as isfrequently the case in hard water with soaps or Turkey red oils does,not take place with these products.

The compounds containing the at least quad ruple polyglycol radicles arealso suitable as disusual methods, may be brought into reaction with'basic compounds, such as amines, acid amides, 115.

black, solid and liquid hydrocarbons, and they may also beadvantageously used as softening agents as for example for films, bandsand lacquers prepared from cellulose esters and ethers or fromartificial resins. Most of the said condensation products may also beadvantageously compounds, such as azo dyestuffs, are prepared in thepresence-of the said products, the said insoluble compoundsare much morefinely divided than when produced in the absence of the said products.

For treatments of textiles in aqueous baths, such as dyeing, washing,scouring, stripping, vivifying or degumming, the amount of the saidcondensation products is usually from 0.05 to 10 grams per each litre ofthe bath.

For the production of pastes, creams, cosmetic preparations, emulsionsor suspensions, the amount of the'said condensation products may be fromabout 5 to about 1000 per cent of the weight of the other ingredients,or more, according to the nature ofthe substances treated and therequired consistency of the final mixture.

The products according to the present invention may be used alone ortogether with other agents, such as alkali metal, ammonia or amine soapsor soap-like substances, for example sulphonic acids of high molecularaliphatic or aromatic hydrocarbons, which may also contain hydroxyand/or carboxylic groups or sulphuric esters of high molecular alcohols,fatty, i. e. vegetable and animal, oils and fats, natural and syntheticwaxes or cellulose esters and ethers. For example preparations from thesaid products and soaps, Turkey red oils, saponine, organic aliphatic oraromatic sulphonic acids, glue, vegetable mucilages, dextrin and othercolloids, salts, such as common salt, Glaubers salt, magnesium sulphateor organic solvents, bleaching agents, such as perborates have veryvaluable properties.

The following examples will further illustrate how this invention may becarried out in practice but the invention is not restricted to theseexamples. The parts are by weight, if not otherwise stated.

Example 1 200 parts of a mixture of higher alcohols, such as "isobtained by the catalytic hydrogenation of vegetal, i. e. animal andvegetable, oils or fats by means of hydrogen at a temperature from about250 to 300 C. in the presence of a finely divided nickel catalyst,consisting mainly of alcohols of the formula CsHr'iOH to C1sH37OH,whereby about 50 per cent of dode'cyl alcohol is present, are heated toabout 180 C. in an autoclave with about 400 parts of ethylene oxidewhich is introduced a little at a time. The ether prepared in this wayhas wetting, washing and emulsifying action as well as protectivecolloid properties and is eminently suitable for washing suint wool andwoolen piece goods. For example if 10 grams of suint wool are treatedfor hour at 45 C. in a bath containing 3 grams of the said condensationproduct per litre of water, a very well cleansed wool having anagreeable soft touch is obtained.

The product is also miscible with solvents, as for example ethyleneglycol mono-cresyl ether, tetrahydronaphthalene, carbon tetrachlorideand like organic water-insoluble solvents, and by the addition of waterto the mixtures, very good emulsions of the said solvents are obtained.Likewise by adding the said products, as for example 10 per cent, tomineral lubricating oil, paraflin oil or other mineral or fatty oilswhich are insoluble in water, they-may readily be rendered capable ofbeing emulsified in water. I

The wetting action of the product may be still further increased by theintroduction of sulphonic groups for example by means of chlorsulphonicacid. The product may also be advantageously employed, inter alia, incarbonizing baths.

Example 2 1.06 kilograms of diethylene glycol are heated to 150 C. in anautoclave and then 8.8 kilograms of ethylene oxide are added a little ata time. The pressure is about 10 atmospheres. After the whole of theethylene oxide has been introduced, the autoclave is heated until thepressure has practically disappeared. A quantitative yield of acolourless water-soluble condensation product is obtained.

A mixture of 3 parts of the condensation product and 1 part of oleic orricinoleic acid is I.

heated to about 130 C. The resulting ester is soluble in water and isnot precipitated from aqueous solutions by salts of calcium, aluminium,copper, zinc or by organic and mineral acids. It has a good foamingpower and washing, wetting and emulsifying action. For example if thecondensation product be mixed with olive oil, whereby the addition maybe less than 10 per cent, a fine and stable emulsion is obtained afterdilution with water.

The product has an excellent washing action and isespecially suitablefor washing suint wool or woolen piece goods. It may also beadvantageously employed, inter alia, as an addition to desizing liquors.The usual desizing agents, as for example vegetable amylases, such asmalt amylase, for example that known in the trade under the registeredtrade-mark Diastafor, or animal amylases, such as an extract from thepancreas gland, for example that known in the I trade under theregistered trade-mark "Degomma, have an optimum effect in acid orneutral baths. Alkaline baths are disadvantageous, and it is only with aconsequent injury to the desizing effect that alkaline washing agentssuch as soap can be added. The addition of a washing agent in additionto the ferment for degrading the starch is often desirable, however,when the material concerned contains fats and oils as well as starch andthis requirement of practice is met by the products according to thepresent invention, such as that described in the foregoing.

5 parts of the said product are added to a desizing bath which contains1 part of an extract from the pancreas gland for example that known inthe trade under the registered trademark Degomma DL for each 1000 partsof water and which has a pH value of from about 6 to 7. The washingaction of the product is fully exerted without the starch-degradingaction of the pancreas gland extract being checked.

' When the same amount of soap is added to the bath it assumes a pHvalue of from 9.0 to 9.3 and the desizing efiect is consequentlyconsiderably impaired.

Example 3 10 molecular proportions of ethylene oxide are added on to onemolecular proportion of the mono-ethyl ether of di-ethylene glycol(C2H5O.CH2.CH2.O.CH2.CH2.OH, obtainable by acting with ethylene oxide onthe mono-ethyl ether of ethylene glycol) in the manner as described inExample 2. 100 parts of the resulting ether are heated with 30 parts ofpalmitic acid for about 12 hours at 150 C. A reaction product of theconsistency of ointment is obtained which is soluble in fats and waterand which is the palmitic ester of the aforesaid ether. For example if 2parts of Japan wax be fused with 1 part of the said palmitic ester ofthe corresponding stearic ester until a clear solution is formed, anemulsion is obtained by slowly adding about 15 parts of hot water whilestirring or shaking, which contrasted with the emulsions prepared withthe aid of soda and soaps has the advantage of being neutral. Moreoverno saponification of the wax takes place.

Example 4 An acetate silk fabric is treated at room temperature forabout 10 minutes with 2 parts of the substance specified in Example 3and 1 part of 10 per cent of formic acid for each 1000 parts of water.The fabric is centrifuged or squeezed and dried at from about 45 to 60C. The fabric acquires a soft, and at the same time crisp, silky touchby this treatment. contrasted with the usual process for producing thecrisp touch, which consists in treating the fabric in a soap bath withsubsequent treatment in a bath of formic or lactic acid, the said methodhas the advantage of comprising only one operation.

Example 5 4 parts of the ester obtained according to Example 2 or theanalogous ricinoleic ester, are added to a mixture of 30 parts of oleicand parts of arachis oil. After the emulsifying agent has been welldissolved in the oil mixture, preferably by warming, the whole is pouredinto 80 parts of water which contains 4 parts of hydroxyethyl methylcellulose dissolved therein while diluted with water to form a 10 percent emulsion. example for greasing wool.

The said ester or the ether alcohol obtained according to Example 1 maybe employed as such or in conjunction with for example petroleum, byreason of their fatty character, their solubility in water and theirwashing and emulsifying action, as a textile oil in the working up ofartificial silk without giving rise to subsequent inconvenience duringdyeing. Similarly, by reason of the said properties, they are eminentlysuitable as such or in conjunction with other oils as greasing agentsfor the working up of animal or vegetable fibres.

Example 6 3 parts of a condensation product from 1 molecular proportionof diethylene glycol and 10 molecular proportions of ethylene oxide areesterified with 1 part of oleic acid in the manner described in Example2, 10 parts of the ester thus obtained are added to 100 parts ofneatsfoot oil, the whole being made into a 30 per cent emulsion withwater by means of a stirring apparatus. The emulsion which may bediluted to any desired extent, possesses very good properties and issuitable, inter alia, for greasing leather. The first-mentioned productmay also be employed as such as a softening agent for leather.

In the preparation of the emulsion of neats-foot oil, the inverse ordermay be followed by dissolving the emulsifying agent in water andallowing the oil to flow into the solution while stirring continuously.

Example 7 Cotton yarn is mordanted in the usual manner with tannin andtartar emetic and dyed in the usual manner with 1.5 per cent of AuramineO (Schultz, Farbstofftabellen 6th Edition No. 493) with an addition toeach litre of the dye-bath of 1 gram of the ether obtained by the addingon of molecular proportions of ethylene oxide to 1 molecular proportionof 7.18-octodecandiol in the presence of 1 per cent, byweight of theoctodecandiol, of caustic soda, in the manner described in Example 2.The 7.18-octodecandiol may be obtained for example by catalyticreduction of castor oil. The addition of the wax-like water-solubleproduct obtained by the adding on of ethylene oxide imparts to the bathan excellent capacity for wetting and in no way injuriously affects thedyeing by reason of the formation of lakes with the dyestuil' such as isusually the case with wetting agents containing sulphonic groups, as forexample alkylated naphthalene sulphonic acids.

'The condensation product is eminently stable to lime and alumina. Itmay be added to indigozinc-lime vats or other indigo vats or to couplingbaths for naphthols, for example to coupling salts which containaluminium compounds in addition to the diazonium compounds, without theformatlon of precipitates. The resulting dyeing is considerably improvedas regards its fastness to rubbing, so that the usual subsequenttreatment with soap may be dispensed with. Likewise it remains insolution in acid baths, even in those of high concentration. The goodstability of the product to all k'nds of electrolytes allows of itsemployment not only in neutral, but also in acid or alkaline printingpastes and in dyeing with aniline black.- Since the product does notform insoluble precipitates with basic dyestuffs, it may v.gorouslymoving the bath, the whole then being b added most advantageously toSolutions of The emulsion is eminently suitable for dyestuffs Example 8molecular proportions of ethylene oxide are added on to the mono-ethylether of di-ethylene glycol in the manner described in Example 3. 100parts of the reaction product are heated with parts of castor oil and3.5 parts of the resulting oily ester are added to a solution of '7parts of a collodion cotton (the solutions of which in organic solventshave a high viscosity) in 40 parts of butyl acetate, 20 parts ofbutanol, 20 parts of ethyl alcohol and 20 parts of benzene. Theresulting solution is employed for pouring films, the resulting filmshaving very good mechanical properties and very good fastness to light.

Example 9 10 parts of a collodion cotton which dissolves in organicsolvents with the formation of solutions of low viscosity are dissolvedin a mixture of 40 parts of butyl acetate, 10 parts of butanol and 30parts of toluene. To this solution are added 5 parts of a conversionproduct from equal amounts of castor oil and the ester obtained from 1molecular proportion of diethylene glycol and 10 molecular proportionsof ethylene oxirle in the manner described in Example 2, and 2.5 partsof an artificial resin obtained from methylcyclohexanone bypolymerization with methylalco- Example 10 150 parts of water containing30 parts of the ester obtained from equal parts of coconut fatty acidsand the condensation product from 1 molecular proportion of diethyleneglycol and 10 molecular proportions of ethylene oxide (obtainable asdescribed in Example 2) and also containing 10 parts of ethylene glycolmonocresyl ether are introduced into a homogenizing appa ratus such as aturbo-mixer of colloid mill. A solution of 200 parts of an ethyleneglycol ester of the acids of oxidation-bleached Montan wax (obtainablefor example according to the U. S. application No. 247,454 filed January17th, 1928) in 400 parts of oil of turpentine are added and the whole isemulsified for from 2 to 5 minutes while adding 450 parts of water, thetemperature being kept near the melting point of the wax. A goodemulsion is obtained which may be applied to leather, wood or othermaterials and yields a highly glossy coating on the said materials afterpolishing or brushing. I

Example 11 water containing 20 parts of the reaction product describedin Example 2, and then a further 200 parts of water are added. Theresulting emulsion is suitable as a basis for intaglio printing inks.

The emulsion may also be prepared by dissolving the emulsifying agenttogether with the asphalt in xylene and emulsifying the said solutionwith the necessary amount of water in a homogenizing apparatus. A

Alternatively, a part of the emulsifying agen may be dissolved in theasphaltic xylene solution and the remainder in water.

Example 1 18 molecular proportions of ethylene oxide are added onto 1molecular proportion of octodecylamine by heating in an autoclave toabout 150 C. A Water-soluble product having a very good wetting power isobtained, which possesses also a good levelling effect in dyeing withvat or acid dyestufis. Thus for example an addition of from 0.1 to 0.2gram to each litre of a dyebath from Indanthren blue green Bfurnishesuniform shades on bleached mercerized cotton fabrics,

whereas without the addition bad dyeings are obtained.

Hydroxyethyl octodecylamine, obtainable for example by the conversion ofthe sulphuric ester of octodecyl alcohol with hydroxyethylamine, mayalso be used as the initial material and the salicylic salt of theproduct may be used as an addition to dressing preparations.

If one molecular proportion of the mono-oleic or -stearic esters oftriethanolamine or of oleic or naphthenic amides be brought intoreaction with from 4 to 10 molecular proportions of ethylene oxide,water-soluble products are obtained which may be employed as sizing ordressing agents or in bowking.

If about 12 molecular proportions of ethylene oxide are added on to forexample triethanol amine and the resulting product is esterifled forexample with oleic acid a product is obtained which may be added forexample to machine oils as an emulgator.

Example 13 From6 to 9 molecular proportions of ethylene oxide are addedon to 1 molecular proportion of octodecyl alcohol, the product beingsulphonated with equimolecular proportions of chlorsulphonic acid whilecooling to from 0 to 25 C.

If 3 parts of one of the resulting acid sulphuric esters in the form ofits neutral sodium salt be added to 1000 parts of water, an excellentwashing effect is obtained with suint wool when treating the same for,4; hour at from 45 to 50? C. in the said bath while keeping the ratioof wool tobath at 1:50. The same result is obtained even after using thebath several times. When artificial silk is treated with watercontaining from 1 to 2 parts of the said product per 1000 parts, itacquires a pleasant supple touch. I

Example .14

10 parts of crude Milan tram silk are degummed at 65 C. with 0.5 part ofpapain, 1.5 100 parts of sodium thiosulphate, 0.5 part of hydrosulphiteand 1 part of the condensation product described in Examples 7 or 2 in1000 parts of Water. The addition of the wetting agent efiects a morerapid wetting and dissolution of the dif- 105 ficultly soluble papainwithout checking its action, such as is the case for example with Turkeyred oils or naphthalene sulphonic acids or other wetting agentscontaining sulphonic groups.

Example 15 From 5 to 10 per cent of the reaction product obtainableaccording to Example 2 are dissolved in 100 parts of boiling linseedoil, which may also contain siccatives, the solution being slowly 115diluted with warm water while stirring. The resulting emulsion is verystable and is eminently suitable for example for sizing or dressingartificial silk or for the preparation of coatings on wood and othermaterials.

Example 16 From 3 to 5 per cent of the product obtained according toExample 7 are added to a commercial Marseilles soap. The soap becomesstable to lime after this addition and is not precipitated even in waterfor example of 20 hardness (German scale).

Emample 17 Example 18 of oleic acid, castor oil, ricinoleic acid orMontan wax carboxylic acids may be employed whereby waxy, from easilyemulsifiable to water-soluble products are obtained.

Example 19 From 660 to 880 parts (from 15 to 20 molecular proportions)of ethylene oxide are led, while stirring at a temperature between 130and 140 0., into 270 parts (1 molecular proportion) of octodecyl alcoholcontaining 2.7 parts of an aqueous caustic soda solution of 40 Be. Theether thus prepared solidifies into a waxy mass on cooling; the productis soluble in most of the usual organic solvents and dissolves veryreadily in water.

The ether possesses an excellent leveling power in dyeing with vat dyesand particularly promotes the thorough dyeing of mercerized pearl yarnand of silk yarn for embroideries in dyeing the said materials with vatdyes. If, for example, mercerized pearl yarn or strongly twisted viscoseyarns be dyed in the usual manner with 5.5 per cent, calculated withreference to the weight of the yarn, of Indanthren blue RS double paste(Schultz, Farbstofitabellen, 1931, No. 1228) with an addition of 5 gramsof the said wax-like ether per each litre of the dyebath, very evenlyand thoroughly dyed yarns are obtained.

If, for example, artificial silk, for example cupro-ammonium silk, bedyed in the usual manner with 0.5 per cent, by weight of the silk, ofIndanthren brilliant violet RR double paste (Schultz, Farbstofltabellen,1931, No. 1265), or with a combination of 0.5 per cent, by weight of thesilk, of Indanthren blue RS double paste (Schultz, Farbstofftabellen,1931, No. 1228) and of 0.5 per cent of Indanthren yellow 3 RT doublepaste (Schultz, Farbstoffstabellen, 1931, No. 1242), with an addition offrom 0.1 to 0.5 gram of the said ether per each litre of the dyebath,very evenly and thoroughly dyed silk is obtained, the quality of thedye-bath being moreover maintained through a long period of time.

If the said ether be added to diazo-solutions in fixing azo dyestuffs onfibres, the solidity to rubbing of the dyes is considerably improved.

The said wax-like ether dissolves in warm oleic acid to form a limpidsolution. If a solution of, say, 2 to 5 parts of the ether in 100 partsof oleic aicd be slowly stirred into water, a stable emulsion isobtained which may be employed for example for oiling textiles.

If from about 8 to 12 molecular proportions of ethylene oxide be addedon, similarly as described ,above, to 1 molecular proportion of decanolor dodecanol or of a mixture of alcohols obtainable by catalyticallyreducing coconut oil or palm 'oil by means of hydrogen, colourlesswater-soluble oils or semi-solid masses are obtained, which possess agood wetting power in alkaline, neutral or acid aqueous baths and whichare not precipi-' tated from aqueous solutions by calcium, magnesium orheavy metal salts. The said oils or semisolid masses may be employedWhenever a wetting agent is needed; they may also be employed asadditions to moistening preparations, for example for moisteningcotton-yarn before weaving, or to preparations for combating pests. Thesaid oils and masses act as protective colloids and possess aconsiderable dispersing power; if the said oils or masses be added tosoap solutions in which calcium salts of the water have precipitatedcalcium soaps, the said calcium soaps are completely dissolved.

By adding from 5 to 6 molecular proportions of ethylene oxide on to 1molecular proportion of cetyl alcohol, products are obtained which maybe usefully employed for imparting to artificial silk, such as thatprepared from viscose, the crisp touch of natural silk. If the saidproducts be heated at 120 C. for 2 to 3 hours in vacuo with their ownweight of a wax-like product, obtained by polymerizing ethylene oxide ata temperature between about 50 and 60 C. by means of an aqueous solutionof caustic potash a product is obtained which possesses a very goodlevelling power in dyeing with vat dyes.

Example. 20

1 part of the mixture of alcohols of high molecular weight, obtained byseparating the unsaponifiable constituents of a product of thedestructive oxidation of parafi'in wax according to Example 1 of theBritish specification No. 303,281 is heated with 2 parts of ethyleneoxide and 0.5 per cent, by weight of the alcohols, of the bleachingearth traded under the registered trade-mark Tonsil 3B in an autoclaveto from to C. until the product has become soluble in water. A thick oilis obtained which possesses a good wetting-out power.

Example 21 ,1 part of wool fat is heated for 3 hours with 2 parts ofethylene oxide and 0.5 per cent, by weight of the fat, of a powderedbleaching earth consisting of aluminium hydrosilicate which containssmall amounts of calcium hydroxide in an autoclave to 100 C. Asalve-like, water-soluble product is obtained which may be used as aneflicient dressing agent.

Example 22 1 part of glycerol mono-oleic ester is heated at from 100 to150 C. in a closed vessel with 2 parts of ethylene oxide. The resultingether of the ester, which is a yellowish rather thick oil, forms acolloidal solution with water and may be employed in oiling textilematerials of any kind in spinning, carding, weaving or other processesand as a lubricant. In the place of the oleic ester the correspondingester mixture of the acids of Montan wax may be employed, massesresembling bees wax being thus obtained.

Example 23 88 parts of ethylene oxide are introduced at 120 C. into 51parts of the mixture of alcohols obtained by the saponification of spermoil and containing 1 per cent of caustic soda or of sodium ethylate. Aproduct is obtained which possesses a high wetting and levelling powerand which is capable of easily emulsifying waxes or waxy compounds asfor example Japan wax or esters of the acids of crude or bleached Montanwax as for example the glycol esters.

If 25 or 12 parts of the alcohol mixture be employed instead of 51 partsvaluable products are equally obtained the solubility of which in wateris still higher than that of the aforesaid product. Mixtures of theaforesaid products with natural waxes, paraffin wax or like waxymaterials can be easily emulsified in water, especially in conjunctionwith organic solvents, such as turpentine oil or benzene. The emulsionsobtained in this manner may be employed as boot or fioor polishes orsimilar polishing preparations.

Eztample 24 20 molecular proportions of ethylene oxide are added on to 1molecular proportion of octodecylalcohol containing 0.5 per cent, byweight, of caustic soda. After leading 1 per cent of hydrochloric gasinto the condensation product, 0.5 molecular proportion of acetaldehydeis dropped in for each molecular proportion of the condensation productin the course of about 4 to 6 hours, while stirring under a refluxcondenser. The water formed by the reaction and any hydrochloric acidpresent are removed by distillation in vacuo, and the remaining productis neutralized, if necessary, by means of soda. An oil is obtained whichis a good plastifying agent for textiles.

Example 25 From 4 to 6 molecular proportions of ethylene oxide are addedon to 1 molecular proportion of octodecyl alcohol in the presence of 1per cent of caustic soda. The product obtained is very useful for theproduction of pastes and creams.

12 parts of the said condensation product are mixed at from 50 to 60 C.with 18 parts of vaseline and 10 parts of paraffin oil; 60 parts ofwater are slowly stirred into the mixture while cooling to roomtemperature. An excellent skin cream is thus obtained. A skin cream mayalso be prepared for example by mixing 10 parts of the said condensationproduct with 20 parts of paraffin oil, 3 parts of peanut oil and 6'?parts of water. i

Example 26 By acting with 1 molecular proportion of chlorosulphonic acidon 1 molecular proportion of the condensation product obtained accordingto Example 25 from 1 molecular proportion of octodecylalcohol and 4molecular proportions of ethylene oxide, the water-soluble, acidsulphuric ester is obtained which is neutralized with caustic soda orpotash, ammonia or an alkylol amine, such as mono-ethanolamine. Thesalts are excellent scouring agents for loose wool.

What we claim is:-

1. The process which comprises condensing a water-insoluble, monomeric,organic compound, selected from the group consisting of hydroxyl,carboxyl and amino compounds containing at least 6 carbon atoms and onereactive hydrogen atom, with a polyglycol compound containing at leastfour ethenoxy groups.

2. The process which comprises condensing a water-insoluble, monomeric,organic compound, selected from the group consisting of hydroxyl,carboxyl and amino compounds containing at least 6 carbon atoms and onereactive hydrogen atom, with a polyglycol compound containing from 6 to50 ethenoxy groups.

3. From readily to difficultly water-soluble derivatives ofwater-insoluble, monomeric, organic compounds, selected from the groupconsisting of hydroxyl, carboxyl and amino compounds containing at least6 carbon atoms, which derivatives contain a polyglycol radicle with atleast four ethenoxy groups.

4. From readily to difficultly water-soluble derivatives ofwater-insoluble, monomeric, organic compounds, selected from the groupconsisting of hydroxyl, carboxyl and amino compounds containing at least6 carbon atoms, which derivatives contain a reactive hydrogen atom,which derivatives contain the group (-OC2H4)n-OX in which OX denoteseither a hydroxyl group, an

ether radicle or an ester radicle and n denotes an integral number above3.

5. From readily to difficultly water-soluble derivatives ofwater-insoluble, monomeric, organic compounds, selected from the groupconsisting of water-insoluble alcohols, carboxylic acids and aminocompounds containing at least 6 carbon atoms and one reactive hydrogenatom, which derivatives contain the group (O-CzH4)n-OX in which OXdenotes either a hydroxyl group, an ether radicle or an ester radicleand n denotes an integral number above 3.

6. From readily to diflicultly water-soluble derivatives ofwater-insoluble aliphatic organic compounds selected from the groupconsisting of water-insoluble alcohols, carboxylic acids and aminocompounds containing at least 6 carbon atoms and one reactive hydrogenatom, which derivatives contain the group (O-C2H4) n-OX in which OXdenotes either a hydroxyl group, an ether radicle or an ester radicleand n denotes an integral number above 3.

'7. Readily water-soluble derivatives of water-insoluble aliphaticorganic compounds selected from the group consisting of water-insolublealcohols, carboxylic acids and amino compounds containing at least 6carbon atoms and one reactive hydrogen atom, which derivatives containthe group (o-C2H4)n-OX in which X denotes a radicle of a polybasicmineral acid and n denotes an integral number above 3.

8. From readily to diflicultly water-soluble derivatives ofwater-insoluble, aliphatic organic compounds selected from the groupconsisting of water-insoluble alcohols, carboxylic acids and aminocompounds containing at least 6 carbon atoms and one reactive hydrogenatom, which derivatives contain the group in which OX denotes either ahydroxyl group, an ether radicle or an ester radicle and n denotes anintegral number from 6 to 50.

9. From readily to difiicultly water-soluble ethers of water-insoluble,aliphatic alcohols containing at least 6 carbon atoms, which etherscontain the group (O-C2H4)nOX in which OX denotes either a hydroxylgroup, a monoalkyl or arylether or ester radical and n denotes anintegral number above 3.

10. From readily to difiicultly water-soluble ethers of water-insoluble,aliphatic polyhydrlc alcohols containing at least 6 carbon atoms, whichethers contain the group (-OC2H4)n-OX in which OX denotes either ahydroxyl group, a monoalkyl or arylether or ester radical and n denotesan integral number above 3.

11. From readily to difiicultly water-soluble ethers of water-insolublemixtures of aliphatic alcohols containing from 10 to 30 carbon atoms,which ethers contain the group in which OX denotes either a hydroxylgroup, a monoalkyl or arylether or ester radical and 11. denotes anintegral number above 3.

12. From readily to difiicultly water-soluble ethers of water-insolublealiphatic alcohols containing from 10 to 30 carbonatoms, which etherscontain the group (--OCzH4)n-OX in which OX denotes either a hydroxylgroup, a monoalkyl or arylether or ester radical and n denotes anintegral number above 3.

13. From readily to difiicultly water-soluble ethers of water-insolublealiphatic alcohols containing at least 6 carbon atoms, which etherscontain the group (OC:H4)OH. inrwhich n denotes an integral number from6 to 50.

14. Neutralized from readily to difflcultly watersoluble ethers ofwater-insoluble aliphatic alcohols containing at least 6 carbon atoms,which ethers contain the group (-O-C2H4)-.OX, in

which X denotes a radicle or an acid and 11 denotes an integral numberfrom 6 to 50.

